Dehydrogenation process and catalysts therefor



FEED TEMPERATURE,F.

FEED TEMPERATURE,F.

June 15, 1965 MuLAsKEY E-rAl. 3,189,661

DEHYDROGENATION PROCESS AND CATALYSTS THEREFOR Filed NOV. 25, 1960 BUTANE DEHYDROGENATION WITH CATALYST'B (D U) i IL Zi 1200 D m -ao O lV 25 z 9. D 05 |--1wEEK l 4 MoNTHs-l Y 2o 5 l l l l z l .l l l lI l 8 3o so 9o 12o 15o DAYs oN STREAM l. B FIG. 1

(l) U) BuTANE DEHYDRoGENA-noN E wm-l cArALYs-r PREPARED As 1N EXAMPLE 1 {j} |200- 35 `ER'ON 1150- m -ao o 11oo- '25 Z 1050- i I 2o 1-2 wEEKs |1o wEEKs l l l I l ao so 9o 12o 15o DAYS oN STREAM FIG. 2

INVENTORS w1'.% coNvERslo United States Patent Oiiice 3,189,561 Patented June 15, 1965 3,189,661 DEHYDROGENATION PROCESS AND CATALYSTS '.lEEREFR Bernard F. Mulaskey, El sobrante, Robert H. Lindquist,

Berkeley, and Hugh F. Harnsberger, San Anselmo, Calif., assignors to California Research Corporation, San Francisco, Calif., a corporation of Delaware Filed Nov. 25, 1960, Ser. No. 71,821

3 Claims. (Cl. 266-680) This invention relates to the preparation and use of supported Group VI metal oxide dehydrogenation catalysts. In particular, the invention is concerned with the use of a chromia-alumina catalyst of unusual properties in the dehydrogenation of aliphatic hydrocarbons containing 2-5 carbon atoms to the molecule for the preparation of the corresponding oleiins and diolelins.

A dehydrogenation process of great interest at the present time is the production of butene and butadiene from butane. The butane dehydrogenation process nding widest acceptance commercially is the so-called adiabatic cyclic fixed bed process, wherein normal butane at elevated temperatures of 900-1200 F. is passed at subatmospheric pressures in the range 1-10 p.s.i.a. through a bed of chromia-alumina catalyst particles preheated to 4the reaction temperature, at a space velocity of 0.5-3 v./V./hr. (volumes of butane per volume of catalyst per hour). Usually, heat retentive catalytically inert refractory solids are mixed with the catalyst, the heat required for the endothermic dehydrogenation reaction being abstracted from the preheated catalyst and inert solids. The temperature of the catalyst bed decreases as it gives up heat absorbed by the reaction, and at the same time a carbonaceous deposit or coke .is laid down on the catalyst. The Ifeed is stopped after an on-stream period or" 5-30 minutes. The bed is then contacted with a heated stream of oxygen-containing gas for an equivalent length of time, which serves to burn off the carbonaceous deposit and thereby to restore the bed to the initial elevated temperature, whereuponV the cycle is repeated. Patent No. 2,474,014 to l. E. Seebold describes procedures for carrying out the regeneration step.

As a modification of the fixed bed process it has been proposed to conduct the operation using a xinely divided catalyst and providing for the requisite short Contact time between the feed and catalyst by use of a transfer line reactor. The entrained catalyst is separated, regenerated by combustion `of the deposited coke to raise the catalyst temperature, and then admixed with additional fresh feed, the catalyst again serving to supply the endothermic reaction heat. In either process scheme the catalyst is alternately and repeatedly exposed at frequent intervals to hydrocarbon vapors under conversion conditions and to oxygen containing gases under regeneration conditions. The processes are applicable to the catalytic dehydrogenation of aliphatic hydrocarbons having 2-5 carbon atoms to the molecule.

Under such severe conditions of alternate reaction and egeneration at frequent intervals, the catalysts heretofore used decline rapidly in dehydrogenation activity. If only moderate temperatures are used and low conversion rates are accepted, the process may be kept ori-stream for 8-12 months. Typically, however, under optimum conditions the maximum catalyst life heretofore has been 3-6 months, rarely exceeding 5 months. The expense involved in replacing the catalyst at such intervals is a major cost factor in the process. Accordingly, it would be highly desirable to be able to extend the period of time for which the catalyst has high activity,'whereby thetime between catalyst replacements could be extended.

` It is an object of this invention to provide a dehydrogenation catalyst which maintains its high activity under Von-stream portion of the process cycle.

the rigorous conditions of alternate reaction and regeneration. Another object is to provide an active dehydrogenation catalyst which is not overly active initially but which is characterized by increasing activity during the initial period of use yand which maintains high activity for a much longer time than catalysts heretofore used. Still another object is to .increase the per pass conversion of aliphatic hydrocarbons to oleiins by using such a catalyst in the dehydrogenation process.

With these objects in mind the present invention is directed to a process of dehydrogenation with a catalyst which has suppressed or hidden activity, i.e., latent capabilities which are developed during use of the catalyst to counteract the activity decline normally observed heretofore during the operation of the process. Y

By Way of background (although the theory presented is not intended to be limiting), the vast extended surface of a fresh chromia-alumina dehydrogenation catalyst .is pictured as comprising predominantly alumina with numerous small chromia particles distributed thereon and covering only a minor fraction of the alumina surface. Loss of active chromia surface area, and hence activity decline in such catalysts, are believed to be caused by: (a) sintering of the chromia particles into larger clumps which give a smaller total active surface area, and (b) chromia diffusing into the alumina to form solid solutions. Sintering is accelerated by high temperatures in both oxidizing and non-oxidizing atmospheres. Diffusion is Aaccelerated by high temperatures in oxidizing atmospheres. Since in the dehydrogenation process the catalyst is alternately and repeatedly exposed to high temperatures in non-oxidizing atmospheres during the reaction period and to high temperatures in oxidizing atmospheres during the regeneration period, the catalyst declines rapidly in activity. Further, at certain conditions of high temperatures in oxidizing atmospheres Aactive chromia from the clumps is transported onto the alumina surface. By magnifying this transport eifect over and above the sintering Vand diffusion effects, chromia surface area and catalyst activity are increased during use, in accordance with the present invention.

We have discovered that a catalyst of the desired properties can be prepared by treating a high-area alumina support at elevated temperatures for several hours toA reduce the alumina surface area, then impregnating the treated alumina with a chromium compound to provide about 20-4() weight percent Cr2O3 in the finished catalyst, and then heating the impregnated catalyst at an elevated Vtemperature for several hours in anoxygen-free and nonoxidizing atmosphere, such as nitrogen. Preferably, the Acatalyst is also promoted with a small quantity of potassium oxide. The activity and chromia surface area of the resulting catalyst actuallyv increase with age up to a maximum value, and thereafter the catalyst declines in activity and chromia surface area more slowly than do the previously known catalysts.

The final heat treatment of the catalyst in a nonoxidizing atmosphere at elevated temperatures is continued forV a sufficient time tosinter the chromia into clumps larger than would ordinarily be formed as a vresult of normal deactivation. To do this and still have a catalyst of adequate initial dehydrogenation activity requires theuse of unusually high chromia concentrations in the catalyst. The active chromia surface area is reduced below that of ordinary catalysts having lower chromia contents. The chromia clumps then have very little tendency to sinter into larger clumps during the Instead, the Ichromia has an increased tendency to be transported onto the alumina during the regeneration portion of the cycle to cause gradually increasing chromia surface area and activity. Thereafter, the activity declines only as a re- Y U.S. Patent VV2,943,067710 R. l.V Sieg.'

Vshould'hzw'e aY surface area above Vabout*2001nf2/grn.

k'sult of the didusion of chromia into the alumina to form solid solutions', and this' efect is less marked when the active cl'irornia` is initially disposed as larger isolated t Y dehydrogenation process.,V Goodresultsare obtained by clumps on Vthe'alumina, in yaccordance with the inven- Y tion. The treatment under non-oxidizing conditions is also important in that'theformation of Cr.+6r species on YIn the preparation of conventional chrnmia-alumina Y dehydrogenation catalysts heretofore, it has beerrcustornv ary to Vprovide a nishedcalcined catalyst` containing -20 percent CrzOa. Y TheV preparation of chromia-alu-Y mina catalystscontaining up to'40V percent' VCrZOa has Y been previously suggested.V However,l we have .found the catalystV is Vthereby avoided during VVthe preparation.' 'Hexavalent chromium appears to Vbe deleterious 1n ace Ycelerating sintering of the alumina support. Y

once the initial wildness of` suchV a .catalyst has wornV Vbi1?, the dehydrogenation ,activityV declines equally as rapidly as the lower chromiacontent prior-art catalysts.V f

' YIt' appears that at such high chromium levels hexavalent Vchromium formed dur-ing air calcination, i.e., 'as.,CrO3, t acts as aflux which accelerates sintering'of the aluminaV during the Vcalcining step and also during the regeneration phase of Vtherplant operation. Catalysts prepared in accorclai'ice4 with this invention' have'betterzstartup char-v acteristics in Athat the catalystis not'overlyV active initially,l

Y' Similarly, there are referencesin the prior art to theuse of a hydrogen reduction treatment of chromia-'alumina catalysts instead of the usual final air calcination. Howeveriit is'found that when a` conventional chromiaalumina catalyst is Vtreated with hot'reducing gas or nitro- Y gentat ,1600" F. for several hoturs,itheV catalyst isV subthat the unusual properties of ourjnovel catalyst are using superheated steam'at af temperature of VaboutV 1500iA F. forY about 6 hours. VvThearea reduction mayalsofbe Y accomplished by air calcination. .Hou/ever,V the `use of t steam is preferred becau'seythe Vtime required isY less f 'andi/or lower temperatures rnaygbeY employed.V -More.

particularly, the selectivity of the'novel catalystsY disclosed herein for the promotion lof dehydrogenationreactions appears to be enhanced when'stearn is used. Y

pregnated The thermallyV .treated Aalumina .isy thenam with ychromium v,oxide by irnmersion'in a concentratedV Y solution yof chromic acid or a heat .d'ecomposablertfsalh such as chromicnitrate; ammonium dichrornate, and'the i,

like, the solution strength and impregnation time-being t f sufcient to provide`20-40 percent Cr203 on Vthe finished "j catalyst, preferably 25-4() percent Cr2O3. .Catalysis ex: Y, hibiting thedesired propertiesY to the greatest extentljcon-` f Y tain more than percent Cr2O3. Instead `of incorporateA ing the potassium'orY other alkali metal promoter in the preparation of'thealurnina, a smallfamo'untof an alkalij'V Y metalV salt," such as YI Jntassiurri dichromate, may bein.V :eluded in the impregnating solution.4` .Preferablyfthe finished catalyst' contains 10.1?05V weightV percent KZO.Y `As the nal step Vin the Vpreparation of V,the catalyst, 't the impregnated alumina-is heated toY decompose'.theY

Y chromium compound to Cr203tin an oxygen-.freeatmos- Vphere, at temperaturesV of 11700-1700" F'yfor fromnt2i48 hours'. `By'.oxygen-free is'meantthat the'hotjgas must be free of' gases'which could( give QCVrO onthe catalyst. The preferred treating agentis' dry Vnitrogen or t otherinertrgasfbut .hydrogen may alsogbe used; VThe fstantially completely deactivated.' Thus, itris apparent Y iY The hydrous alumina gel used as the star-ting materialV in the preparation Vof the catalyst of Vthis invention may Vbe anyhigh surface area synthetic or natural alumina,Y

Vsuch asboehmite or fbayerite, inthe form of Ysmallpa'rticles orfas apowder. Alternately, the alumina gel .can be. prepared, :for example, lby the addition of ammonium hydroxide or other, alkaline agent VtoV an lacidic aqueous Y solution of Valuminum sulfate,V nitrate,vr chloride, Yor other 1 A' salt.Y rThe resulting hydrogel is then washed and filtered t V'to removesoluble contaminants, andthen dried. to vaY finely'divided powder. If the catalyst is to be promotedV with potassium or otherallrali metal, Vthe powdered alumina may be slurried with Van aqueous solution Vof a heat decomposable alkali metalsalt, .the resulting slurry thenjbeinrgY driedV and formed into pellets, Aextrulates, or similar particles. The activity stabilizing efect ofV alkali metal oxides on chromia-alu'mina catalysts is disclosed in (square 4meters perv gramrfas determined by Vnitrogen adsorption. x t Y.

Thealumina carrier isttherr'n'ally treated by heating The alumina be used ifV longer treating times areremployed.

. observation that canbon monoxide is strongly chemisorbed .by thepcatalytically active transition metalsV andY lower Vvalen-t metal oxides and only weakly adsorbed, or not at t' Y all, by alumina or silica supports. V.The car-.bon monoxide. chernisorptiony data reported .herein were obtained; by a ilowadsorptionV methodY wherein a known gas mixturfepoff; l

Y carbon monoxide V.containing carboni-14 monoxidein he'-Y lium is passed at room temperature and pressure (3 .5 mm.,YV /Hg CO partial pressure)- and at a constant rate over-*aV t weighed pre-reduced kcatalyst V,sample 'inVV equipmentl of Y known Volume'.n FromV the Ytime required :before carbon-'14 f monoxide appears in the effluent helium, Vas'detected byraV Geiger counter, the volume of carbon monoxide adsorbed Y is calculated. VV.The detailed .procedurezis set forth in aV paper entitled,Y fFlow AdsorptionfMethod lfor Catalyst Metal Surface Measurement, presentedat .the'SyrnjgiofY s'ium, Di-vision of Petroleum Chemistry of the`A'.C.SL, in

. Boston, Massachusetts, April 5-l0, V1959, by T. R. Hughes, v

R. VI.V Houstomand RUP. Sieg. The dehydrogenation ac` tivity of chromia-Valumina" catalysts ha's'jbe'en foundftojbe Y Vdirectly 'related to the chromia surface Varea as measuredf pendV upon` the Vproperties nof the :particular alumina. 11n

selecting the proper time and tempera-ture, the condi- Vtions should bes'uch'as to reduce thesurface'area of the alumina `as Vdetermined by nitrogen4 adsorption toV aboutVV 100.` m.2/gm. or less, Vbut'no't below aboutd60 HL2/gm." When the alumina surfaceltarea its below 60 m.2/gm., the

finished catalyst its less active. Higher VareasY than 100 n L/gm, seem to result in excessive coke Vformationin .the

V`lby CQ chemisorption. As-'lfx'ereinbefroreLmentioned,cat-V Y alys't aging Y,anddeactivation in-:the cyclic adiabatiedef Y hydrogenation process is accompaniedby, and appears to; y Vbe caused by,'a reduetionin the active .ehromia surface-1V conditions ofttime and temperature should `be such .asf f Vto reduce the active chromia surface area as determined, .Y by carbon'monoxiderchemisorption vtcy'less lthan 15 micro# moles `of CO per grarn of catalyst, preferably 8-,12 micro- Y moles CO/ The activity of catalysts;` having chromia surface areas` below .aboutV 6 micromoles V CO/giri; is quite low. The conditions should not beso severe'asto result in aY further reduction of the alumina surface area'` 'y Y. as measured by nitrogeri'adsorption .to below about 50 Y V:n2/gm.YV YFor example, goed Vresults' are obtainedfby"Y l treating the impregnated alumina at Val;)out'l60 0Fgfor about 6 hours in nitrogen, but lower temperaturesmay l Measurement of the active `chrornia surface areairi terms of carbon monoxide chemisorption is fbasedjon the Elea.

y The following example'llustrates..the preparation sofia'VY Vcatalyst in accordance with this invention.VV Y Y l 'i EXAMPLE 1 Pour and one-half liters of a preformed hydrous alumina gel in the form of 46 extrusions was contacted with superheated steam at 1500o F. for 6 hours. At the conclusion of .this treatment, the Valumina particles had an average surface area as determined by nitrogen adsorption of 93 rn.2/gm. as compared to an initial surface area of 372 m.2/grn. The alumina particles were then impregnated with chromia by immersion for onerhour in a concentrated solution prepared by dissolving 4440 grams of CrO3 and 65 grams of KOH in 41/2 liters of water. The impregnated particles were drained free of excess solution, and were then contacted with dry nitrogen at 1500" F. for 24 hours. The finished catalyst -analyzed 27 Weight percent Cr203 and 0.28 weight percent K2O, the bala-nce being alumina. The nitrogen surface area was 72 m.2/ gm., and the active chromia surface area was l0 micromoles of CO per gram. The catalyst exhibited the X- ray diffraction pattern of .theta-alumina.

The following example illustrates another preparation of the catalyst using somewhat modified conditions.

EXAMPLE 2 Ten liters of an alumina extrudate having a nitrogen surface area of 402 m.2/g1n. kwas treated with steam at 1500 F. for 7 hours.' The alumina surface area was reduced to 101 nmz/gm. This material was dipped for 3 hours in an aqueous solution of 12,100 gm. CrO3 and 145 gm. KOH in liters of water. 'I'he impregnated ,extrudate was then drained free of excess solution for 2 hours. The material was then exposed to nitrogen at 1400 F. for 6 hours. The finis-hed catalyst contained 29.5% Cr2O3 and 0.16% KZO, by weight, and had a surface area vby nitrogen adsorption of 71 m/ gm. This catalyst will .be found to have a chromia surface area very close .to that of the catalyst prepared in Example -l.

The manner in which catalyst properties and changes therein with age inlluenoe the operation of the butane dehydrogenation process maybe better understood by reference to FIGURE l. This graph represents .typical smoothed data obtained during the operation of a fullscale multiple reactor adiabatic unit using a commercial %2" pelleted dehydrogenation catalyst comprising 2()V percent C12O3 and 80 percent alumina, hereinafter referred to as catalyst B. This unit operates at a pressure of centimeters Hg absolute, withl .a cycle time of 171/2 minutes: 71/2 minutes each on reaction and regeneration, with 21/2 minutesfor purging and valve changes. As indicated on FIGURE 1, the plant is started up .using low butane feed and lair inlet temperatures in order to avoid wild erratic operation. (In this-unit the regeneration air is preheated to the sameinlet temperature as the feed.) lThe temperature issoon raised-to the desired operating level of about 1060 F. Immediately, the catalyst activity begins'to decline, and it is necessary to begin raising the feed inlet temperature in order to maintain a high percentage conversion per pass to butenes, of about 32 percent. After about one Week of operation the feed inlet temper- Iature is at aboutV 1100`F., at which time .the percent conversion to butenes is `still satisfactory. After the catalyst has been in use for about 6 Weeks, the Yfeed and air inlet temperatures reach 1175 F., which is the maximum allowable temperature in this unit. There-after, the catalyst activity continues .to decline, and it is not possible to make furher compensatory adjustment by raising the temperatures. Consequently, .the per pass conversion of butane to butenes drops olf. After about 3 months of operation t-he de'hydrogenation activity of the catalyst has declined relative to the coke-forming .activity such that excessively high-temperatures are reached dur-ing the regeneration cycle. Consequently, it is necessary to begin reducing the feed temperature, to about ll40 F. at about 4 months, further lowering the percent conversion, to about percent, as shown in FIGURE 1. Finally, after 5 months of operation the process has become uneconomiaoV cal, and it is necessary to shut down and replace the catalyst.

The following example presents a comparison of the catalyst of the present invention with catalyst B, illustrating the changes in active chromia surface area occurring dur-ing exposure to such typical operating conditions.

EXAMPLE 3 Samples of catalyst B and the catalyst prepared in Example l were placed within one of the beds of commercial catalyst B in the full scale unit described above, in a small cannister having a height equal to the catalyst bed depth (about 40) In this way the catalyst of the present invention was exposed to exactly the same conditions as catalyst B, but operation of the process Was dictated by the properties of the latter catalyst. Samples of the mixed catalysts were withdrawn from the reactor during the run through a special blow tube installed for that purpose. The active chromia surface area of each catalyst at various time intervals was measured by CO chemisorption. The changes in the properties of the catalysts during use are summarized in the following Table I, from which it is seen that the active chromia surface area of the catalyst of this invention increased during the rst two Weeks of plant exposure and thereafter declined very slowly, whereas the active chromia surface of catalyst B.Was initially higher but declined more rapidly and at all times.

Table l Days, Plant Exposure V 0 7 14 30 70 1 150 Active Chrornja Surface Area.1

#moles CO/gm.:

Catalyst B 14 12 9 8 6 4 Catalyst of Example 1 l0 13 16 15 13 10 1 End of run.

In Example 3, the butane dehydrogenation process was operated for maximum butene yield, using relatively pure butane as the feed. When it is desired to maximize butadiene production, it is advantageous to recycle a major portion of the butenes to the feed.V The unusual properties of the novel catalysts disclosed herein make'their use of particular value in this latter type of operation also. Increasing activity is again observed, and the activity remains high for a longer time than previously known catalysts. To further illustrate the above features, the following example is presented.

EXAMPLE 4 Samples of the catalyst prepared in Example 2 together With samples of catalyst B and another commercial catalyst, hereinafter referred to as catalyst A, comprising Mz extrudate containing 20 percent Cr2O3 and 80 percent alumina, were placed within a bed fof catalyst A. In this way, all three catalysts were exposed to exactly the same conditions, but operation of the process was dictated by the properties of catalyst A. The catalyst beds in the various reactors of the unit comprised a 5 0-50 mixture of catalytically inert alundum balls and catalyst A. Operation was similar to that previously described, except that a 30-minute cycle was used and the butane feed contained about l0 percent n-butene. Samples of each catalyst Were Withdrawn during the rst two months of the run. These samples were then tested in a laboratory micro-reactor under isothermal conditions for direct activity comparisons. The conditions used in the microreactor test were 1050" F., 1 atmosphere pressure, 2 v./v./hr., and l0 minutes each on feed and regeneration cycle. The changes in the activities of the catalysts due to the plant exposure are summarized in the following Table II.

Table Il Days, Plant Exposure Y 15 K 1 2 g Y l Days Month Months Isothermal Microreactor Test: Y

' Wt. Percent Butane ConvertedV Y v Catalyst A 48.1 A 45. 5 42. GV

Catalyst B 52. 46. 3 45.8 45. 4

Catalyst of Example 2 45. 5 48. 3 Y 4S. 8 50. 7

Wt. Percent Conversion to Butenes- Y Catalyst A 3Q. 9 37, 8 V35. 3Y Catalyst B Y 39. 5 37. 4 37. 2 37. 6 Catalyst of Example 36. O 38. 9 38.6 40. 7

Wt. Percent Conversion to Butadit eneu Y Y Y Catalyst A 1. 4 1:6 1. Catalyst B 1. 6 2. 1 1.9 Y 1.- Catalyst of Example 2 1. 9 2. 0 1.'8 V2.

Again, it/is seen that the catalystV prepared in accordance Y with this invention was initially less iactive than either Vof .Y From the above data it is apparent thatY in using theV improved catalysts of the present invention in thebutane dehydrogenation process an entirely diiferent type of op- Y eration may be followed as compared to that shown inV FIGURE l.' Referring to FIGURE 2, it is seen that since Y YY the conventional catalysts, but thatY its dehydrogenation ac-k Y tivity increased during use to a highen level andrernained higher than that of the'other catalysts;

the catalyst is notroverly active initially, it is posisble to bring the Vplant quickly ori-stream at aboutzlOO" F. or higher. During the'rst two weeksV of operation, i.e based on'the data of T ableI, the catalyst is characterized by increasing activity'such that by (maintaining the feed Y r inlet temperature atabout l060 Y1:". an increase in butane Y declines slowly,.maintaining the tempera-tures of butane i vapors and oxygen-icontaininggas belofw about IIYOQLF. f duringsaid initial period of use and thereafter Vfor atleast 1 ten weeks and untilrsaid activity has declined substantially;

samermannerfas the'previouslyused catalysts, although Y at a much slower'rate, and gradually increasing feed inlet temperatures areV resorted to in `order to maintain the desired high percentageconversion. When it is'no longer possible to compensate for the activityvdecline by further i continued (not shown on FIGURE 2). e' Itis found that the Vcatalystsfof the 'present Vinvention' YVcan be kept-in service approximately twice as longhas'the best catalystY heretofore used.VV It is also noted that at all Increased conversion vcould be obtained during that initial Y times after the initial periodi" of use a higher perl pass Vconversion to butenes is obtained. Y

Vtemperature increases, the process Vis continued'at, the

2,706,741 4/55- Sieg et .a1 Y '26068o 2,809,170 10/57= Cornelius'etfal. 252-465 2,857,442 /58 Hay 1 252-7465" V`2,890,162 V6/59 AndersonY et al.Y 252-465 i .2,905,632 9/59 Gladrow et al. 252-465 1 g2,943,067 Y 6/60 Sieg 2527-465. 3,064,062 -11/162 Lorz et al. 2605680 V:period also by raising the temperatureas was done whenV using the conventional catalyst. Thus, the disclosed herein may be used inthe dehydrogenation procintermediate temperatures, We claim:

' 1; A chromia-'alumina dehydrogenation catalyst containing between 25 and 4() weight percent CrZOB', having an active chromia surface area las measured by CO chemisorption of less than micromoles'CO per gram andan alumina surfacearea as measured by nitrogen adsorp-l tion of at least 50 square meters per/ gram, said catalyst Y Y having 'beenjproduced by a method comprising impregnatf: y Y* ing alumina',which was prepared Vby heat treating a high Y surface `area alumina at1V100-1600. F. for 2-24 hours to Y reduce its surface area to between 4about 60 and'about 10Q Y I Y square meters per gram as measured by nitrogenadsorption, withV a chromium compound decomposable to CrZO,V and then heating the chromium-impregnated Yalumina inVY anV oxygen-free .atmosphere atV 1100-1700 F. for 2-48, Vhours to obtain the first-,mentioned chromia andalurninak surface areas. Y Y 1 `Y i 2. The'catalyst of claim k1 Icontaining between 0.1 'and 0.5 weightpercent KzO.

3, A p-rocessffor the dehydrogenation V'of'rbutane toVV butenes andbutadiene which comprises passing alternately and repeatedly through a bedrof'aV catalyst of 'claim 1,

rst, butane vaporsat 900-1100 F. `and 1-10 p.s.i.a.to

dehydrogenate butane and to deposit coke on the catalyst,

and second, anrvoxygen-containing gas'at 90W-1100D F, to Y remove deposited coke by combustion causing elevation of the bed temperature, whereby the dehydrogenationac'- Y Y tivityv of said .catalyst increases during Van initial periodof use, thereafter V`remains relatively stable, and ultimately then increasing Vsa-id temperatures gradually towardsA '1200? F., land continuing alternately' andA repeatedly passing-.v` p Vbutane vapors and oxygen-containing gas fora periodin excess of iive months .at a per passconversion .of butaue Y to butenes in excess of VvIieferenc:es Cited by theExamrer Y UNITEDD STATES PATENTS Y ALPHoNsoDj SULLIVAN, Primm Examinar,.-

novel catalysts Y 

1. A CHROMIA-ALUMINA DEHYDROGENATION CATALYST CONTAINING BETWEEN 25 AND 40 WEIGHT PERCENT CR2O3, HAVING AN ACTIVE CHROMIA SURFACE AREA AS MEASURED BY CO CHEMISORPTION OF LESS THAN 15 MICROMOLES CO PER GRAM AND AN ALUMINA SURFACE AREA AS MEASURED BY NITROGEN ADSORPTION OF AT LEAST 50 SQUARE METERS PER GRAM, SAID CATALYST HAVING BEEN PRODUCED BY A METHOD COMPRISING IMPREGNATING ALUMINA, WHICH WAS PREPARED BY HEAT TREATING A HIGH SURFACE AREA ALUMINA AT 1100-1600*F. FOR 2-24 HOURS TO REDUCE ITS SURFACE AREA TO BETWEEN ABOUT 60 AND ABOUT 100 SQUARE METERS PER GRAM AS MEASURED BY NITROGEN ADSORPTION, WITH A CHROMIUM COMPOUND DECOMPOSABLE TO CR2O3, AND THEN HEATING THE CHROMIUM-IMPREGNATED ALUMINA IN AN OXYGEN-FREE ATMOSPHERE AT 1100-1700RF. FOR 2-48 HOURS TO OBTAIN THE FIRST-MENTIONED CHROMIA AND ALUMINA SURFACE AREAS.
 3. A PROCESS FOR THE DEHYDROGENATION OF BUTANE TO BUTENES AND BUTADIENE WHICH COMPRISES PASSING ALTERNATELY AND REPEATEDLY THROUGH A BED OF A CATALYST OF CLAIM 1, FIRST, BUTANE VAPORS AT 900-1100RF. AND 1-10 P.S.I.A. TO DEHYDROGENATE BUTANE AND TO DEPOSIT COKE ON THE CATALYST, AND SECOND, AND OXYGEN-CONTAINING GAS AT 900-1100*F. TO REMOVE DEPOSITE COKE BY COMBUSTION CAUSING ELEVATION OF THE BED TEMPERATURE, WHEREBY THE DEHYDROGENATION ACTIVITY OF SAID CATALYST INCREASES DURING AN INITIAL PERIOD OF USE, THEREAFTER REMAINS RELATIVELY STABLE, AND ULTIMATELY DECLINES SLOWLY, MAINTAINING THE TEMPERATURES OF BUTANE VAPORS AND OXYGEN-CONTAINING GAS BELOW ABOUT 1100*F. DURING SAID INITIAL PERIOD OF USE AND THEREAFTER FOR AT LEAST TEN WEEKS AND UNTIL SAID ACTIVITY HAS DECLINED SUBSTANTIALLY, THEN INCREASING SAID TEMPERATURES GRADUALLY TOWARDS 1200* F., AND CONTINUING ALTERNATELY AND REPEATEDLY PASSING BUTANE VAPORS AND OXYGEN-CONTAINING GAS FOR A PERIOD IN EXCESS OF FIVE MONTHS AT A PER PASS CONVERSION OF BUTANE TO BUTENES IN EXCESS OF 25%. 